EP2542532B1 - Method for preparing carbene in solution and stable form of carbene obtained by said method - Google Patents

Method for preparing carbene in solution and stable form of carbene obtained by said method Download PDF

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EP2542532B1
EP2542532B1 EP11700249.3A EP11700249A EP2542532B1 EP 2542532 B1 EP2542532 B1 EP 2542532B1 EP 11700249 A EP11700249 A EP 11700249A EP 2542532 B1 EP2542532 B1 EP 2542532B1
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group
alkyl
optionally substituted
aryl
alkoxy
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French (fr)
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EP2542532A1 (en
EP2542532B8 (en
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Christian Maliverney
Laurent Saint-Jalmes
Antoine J. BACEIREDO
Tsuyoshi Kato
Sophie GOJON
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Centre National de la Recherche Scientifique CNRS
Elkem Silicones France SAS
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Centre National de la Recherche Scientifique CNRS
Bluestar Silicones France SAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
    • C08F4/80—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from iron group metals or platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used

Definitions

  • the present invention relates to a process for the preparation of carbene by deprotonation of a precursor salt with the aid of a strong base.
  • any singular denotes indifferently a singular or a plural.
  • Platinum / carbene complexes are known as Poly-OrnanoSiloxane (POS) hydrosilylation catalyst with Si-vinyl motifs, by means of POS with ⁇ Si-H motifs.
  • POS Poly-OrnanoSiloxane
  • PCT WO-A-02/098971 describes a crosslinkable silicone composition made of elastomer by hydrosilylation, in the presence of platinum catalysts formed by a C3 or C4 complex:
  • N-heterocyclic carbenes can be used as a cyclic ester polymerization catalyst. More specifically, 1,3-bis- (2,4,6-trimethylphenyl) imidazol-2-ylidene has been tested as a catalyst for the polymerization of L-lactide, ⁇ -caprolactone and ⁇ -butyrolactone, in the presence of an alcohol used as an initiator.
  • a more recent and more complete article (cf. JACS 125, n ° 10 p 3046-3056, 2003 ) describes the carbene preparation in situ to avoid hydrolysis problems.
  • the promoters used are of the thiazolium, imidazolium and imidazolinium type, respectively giving thioazole carbene, imidazol-2-ylidene carbene and imidazolin-2-ylidene carbene catalysts, when they are placed in the presence of potassium tert-butoxide.
  • FR-2864543-A discloses carbenes obtained by deprotonation of an imidazolium salt in the presence of a strong base and used for the synthesis of polyorganosiloxane silicones, by ring opening polymerization (s) and / or redistribution of linear or cyclic polyorganosiloxanes.
  • FR-2900153-A discloses a carbene, dicyclohexyldiaminocarbene obtained by deprotonation of the corresponding imidazolium triflate according to the following operating protocol:
  • This carbene catalyzes the polycondensation of silicone oil type silanols of formula [(CH 3 ) 2 (OH) SiO 1/2 ] - [(CH 3 ) 2 SiO 2/2 ] 10 - [CH 3 ) 2 (OH) SiO 1/2 ].
  • NHC carbenes obtained by deprotonation of an imidazolium salt with a strong base in a THF-type solvent, are then isolated by filtration in order to remove the salt formed and then recrystallize, or even sublimate.
  • the patent EP-1268440-B1 relates to a process for preparing N-heterocyclic carbenes comprising heating a dialkylimidazolium halide with a strong base under reduced pressure.
  • the carbene is distilled during its formation with a horizontal distillation apparatus, possibly distilled with the same apparatus a second time. It can be isolated pure under inert gas or dissolved in an inert solvent (preferably aromatic).
  • carbenes are very reactive species that degrade in the open air, which involves keeping them and handling them under an inert atmosphere (argon or nitrogen). Their synthesis is also obviously conducted under an inert atmosphere and the solvent used is previously dried and freshly distilled.
  • the anion Z 1 - is the anion derived from an organic or inorganic Brönsted acid (protic acid).
  • the anion Z 1 - is derived from an acid having a pKa of less than 6.
  • Z 1 - is derived from an acid of pKa less than 4, more preferably less than 2.
  • the pKa in question here are the pKa acids as measured in water.
  • carboxylic acids are acetic acid, benzoic acid, and stearic acid.
  • sulfonic acid mention will be made of benzenesulphonic acid and, as the preferred phosphonic acid, mention will be made of phenylphosphonic acid.
  • Z 1 - anions derived from HCl, HI and HBF 4 and HPF 6 acids are more particularly preferred.
  • Z 1 - anions according to the invention are halide anions and tetrafluoroborate and hexafluorophosphate.
  • imidazolium salts are given below. These consumables are either commercially available or easily prepared by those skilled in the art from commercial compounds.
  • the nature of the Z1 anion in the salts of formula (III) depends on the acid used in this step.
  • the usable acids are, for example, those listed above and those from which Z1 is derived.
  • the alcohol corresponds to the formula (I °) R ° OH, in which R ° corresponds to an alkyl group; cycloalkyl; aryl; alkenyl; alkynyl; arylalkyl; silyl or siloxane, R ° being preferably selected from the group comprising: methyl, ethyl, propyl, butyl.
  • the strong base according to the invention chosen from the group of hydroxides, alkoxides, hydrides or alkali or alkaline earth metal amides, preferably in the subgroup comprising: CH 3 ONa, potassium tertiobutylate, KOH, NaOH, CH 3 CH 2 OMgOCH 2 CH 3 and mixtures thereof.
  • this strong base can be formed in situ, for example by adding sodium, or sodium hydride, or magnesium in the alcohol in question. This is how alcoholates can be generated in situ.
  • the deprotonation produces a salt which precipitates and which is separated from the solution A,
  • the solvent is sublimed so as to collect the carbene C in solid form.
  • Alkyl means a linear or branched saturated hydrocarbon-based chain, optionally substituted (eg with one or more alkyls), preferably from 1 to 10 carbon atoms, for example from 1 to 8 carbon atoms, more preferably from 1 to 7 carbon atoms.
  • alkyl groups are in particular methyl, ethyl, isopropyl, n-propyl, tert-butyl, isobutyl, n-butyl, n-pentyl, isoamyl and 1,1-dimethylpropyl.
  • the alkyl part of the alkoxy group is as defined above.
  • the perfluoroalkyl group or optionally substituted by a perfluoroalkyl group preferably corresponds to the formula: - (CH 2 ) p -C q F 2q + 1 wherein p is 0, 1, 2, 3 or 4; q is an integer of 1 to 10; and C q F 2q + 1 is linear or branched.
  • Preferred examples of this group are: - (CH 2 ) 2 - (CF 2 ) 5 -CF 3 and - (CF 2 ) 7 -CF 3 .
  • aryl denotes an aromatic hydrocarbon group having from 6 to 18 carbon atoms, monocyclic or polycyclic and preferably monocyclic or bicyclic. It should be understood that, in the context of the invention, a polycyclic aromatic group means a group having two or more aromatic rings condensed (orthocondensed or ortho and peri-condensed) to each other, that is to say presenting, two by two, at least two carbons in common.
  • aryl is optionally substituted for example by one or more C1-C3 alkyls, one or more halogenated hydrocarbon groups (eg CF 3 ), one or more alkoxy (eg CH 3 O) or one or more hydrocarbon groups comprising one or more ketone units (eg CH 3 CO-).
  • aryl mention may be made of phenyl, naphthyl, anthryl and phenanthryl radicals.
  • arylalkyl denotes an alkyl group as defined above, substituted with one or more aryl groups on its hydrocarbon chain, the aryl group being as defined above. Examples are benzyl and triphenylmethyl.
  • Cycloalkyl means a mono- or polycyclic saturated hydrocarbon group, preferably mono- or bicyclic, preferably having from 3 to 10 carbon atoms, more preferably from 3 to 8.
  • Polycyclic saturated hydrocarbon group means a group having two or more cyclic rings attached to each other by ⁇ or / and fused two by two. Examples of polycyclic cycloalkyl groups are adamantane and norbornane. Examples of monocyclic cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • alkenyl is meant a linear or branched unsaturated hydrocarbon chain, substituted or unsubstituted, having at least one olefinic double bond, and more preferably a single double bond.
  • the alkenyl group has from 2 to 8 carbon atoms, more preferably from 2 to 6.
  • This hydrocarbon chain optionally comprises at least one heteroatom such as O, N, S.
  • Preferred examples of alkenyl groups are allyl and homoallyl groups.
  • alkynyl is meant according to the invention, a unsaturated hydrocarbon chain, linear or branched, substituted or unsubstituted, having at least one acetylenic triple bond, and more preferably a single triple bond.
  • the alkynyl group has from 2 to 8 carbon atoms, more preferably from 2 to 6 carbon atoms.
  • This hydrocarbon-based chain optionally comprises at least one heteroatom such as O, N, S.
  • silyl is meant according to the invention, a linear or branched group containing at least one silicon atom.
  • Polydimethylsiloxane chains are examples of silyl groups.
  • the carbenes of formula ( II ) and ( II ' ) may have at least two fused rings, that is to say that at least two groups of T1, T2, T3, T3', T4 and T4 'situated on two vertices adjacent, together form a saturated or unsaturated hydrocarbon chain, preferably having from 3 to 6 carbon atoms.
  • saturated or unsaturated hydrocarbon-based chain means a linear or branched hydrocarbon-based chain which may or may not have one or more olefinic double bond or acetylenic triple bond unsaturations.
  • T3 and T4 are both hydrogen or together form aryl, and more preferably phenyl.
  • the method according to the invention thus gives access to a solution based on alcohol and carbene. Surprisingly and unexpectedly, this alcoholic solution is stable and catalytic.
  • the invention also covers this stable and catalytic carbene per se alcoholic solution obtained by the process according to the invention.
  • the present disclosure relates to a process for the preparation of Polyorganosiloxanes (POS) by ring opening polymerization and / or by POS redistribution and / or by polycondensation, in the presence of a catalyst (C) comprising at least one less a carbene as obtained by the process as defined above, said carbene being in the form of an alcoholic solution or a solid extracted from said liquid.
  • POS Polyorganosiloxanes
  • ring opening polymerization refers to a polymerization in which a cyclic compound (monomer) is opened to form a linear polymer.
  • distributed polymerization corresponds to the meaning of a person skilled in the art of silicone chemistry.
  • the “redistribution polymerization” is understood in the field of silicones, as a rearrangement of organosiloxanes of different structures and / or molecular weight. This rearrangement leads to a single new POS.
  • an alcohol is used directly as solvent for the reaction, allowing instantaneous protection of the carbene as soon as it is formed.
  • the synthesis is carried out in the open air.
  • Example B111 Synthesis from dicyclohexylimidazolium tetrafluoroborate (WO 02/98888 of June 4, 2002) ⁇ sample 1
  • Example B112 Synthesis in THF diluted medium according to the invention (dilution equal to 1) - ⁇ sample 2
  • Example B114 Same reaction as B112 (with THF) with a carbene solution prepared a month ago and stored without precaution at 20 ° C ⁇ sample 4
  • the reaction studied is the hydrosilylation of 1-octene by 1,1,1,2,3,3,3-heptamethyltrisiloxane without solvent:

Description

Domaine de l'inventionField of the invention

Le domaine de l'invention est celui de la synthèse de carbènes et de leurs applications notamment comme catalyseurs ou ligands dans :

  • la préparation de PolyOrganoSiloxanes (POS) par polymérisation par ouverture de cycle et/ou par redistribution et/ou polycondensation de POS,
  • l'hydrosilylation d'au moins un PolyOrganoSiloxane -A- (POS) porteur d'insaturation(s) éthylènique(s) et/ou acétylènique(s), à l'aide d'au moins un polyorganohydrogénosiloxane -B-, ou d'autres composés éthyléniquement et/ou acétyléniquement insaturés,
  • l'hydrogénation,
  • la métathèse d'oléfines,
  • le couplage croisé C-C et/ou C-N,
  • la synthèse asymétrique ou énantiosélective,
  • ou la synthèse organique : réactions d'estérification, trans-estérification, condensation de type aldolisation par exemple.
The field of the invention is that of the synthesis of carbenes and their applications especially as catalysts or ligands in:
  • the preparation of PolyOrganoSiloxanes (POS) by ring opening polymerization and / or by redistribution and / or polycondensation of POS,
  • hydrosilylation of at least one polyorganosiloxane -A- (POS) bearing ethylenic (s) unsaturation (s) and / or acetylenic (s), using at least one polyorganohydrogensiloxane -B-, or other ethylenically and / or acetylenically unsaturated compounds,
  • hydrogenation,
  • the metathesis of olefins,
  • cross coupling CC and / or CN,
  • asymmetric or enantioselective synthesis,
  • or organic synthesis: esterification reactions, trans-esterification, aldol condensation, for example.

La présente invention concerne un procédé de préparation de carbène par déprotonation d'un sel précurseur à l'aide d'une base forte.The present invention relates to a process for the preparation of carbene by deprotonation of a precursor salt with the aid of a strong base.

Dans tout le présent exposé, tout singulier désigne indifféremment un singulier ou un pluriel.Throughout this presentation, any singular denotes indifferently a singular or a plural.

Arrière-plan technologique et problème techniqueTechnological background and technical problem

Les complexes Platine/carbène sont connus comme catalyseur d'hydrosilylation de PolyOrganoSiloxane (POS) à motifs ≡Si-Vinyle, au moyen de POS à motifs ≡Si-H. A titre d'exemple, on peut citer la demande PCT WO-A-02/098971 qui décrit une composition silicone réticulable en élastomère par hydrosilylation, en présence de catalyseurs au platine formé par un complexe C3 ou C4 :

Figure imgb0001
Platinum / carbene complexes are known as Poly-OrnanoSiloxane (POS) hydrosilylation catalyst with Si-vinyl motifs, by means of POS with ≡Si-H motifs. For example, the demand can be cited PCT WO-A-02/098971 which describes a crosslinkable silicone composition made of elastomer by hydrosilylation, in the presence of platinum catalysts formed by a C3 or C4 complex:
Figure imgb0001

Les carbènes utiles en tant que ligands de métaux catalytiques, sont exploités dans d'autres domaines que celui des silicones. Ainsi, le brevet EP-B-0 971 941 décrit des catalyseurs à base de complexes Ruthénium et Osmium/carbène, pour la métathèse thermique de cyclooléfines.Carbenes useful as catalytic metal ligands, are exploited in other fields than that of silicones. Thus, the patent EP-B-0 971 941 describes catalysts based on Ruthenium and Osmium / carbene complexes, for the thermal metathesis of cycloolefins.

En outre, un article de J.L. Hedrick et al paru en 2002, (JACS 124, n° 6 p 914-915, 2002 ), enseigne que des carbènes N-hétérocycliques peuvent être utilisés comme catalyseur de polymérisation d'esters cycliques. Plus précisément, le 1,3-bis-(2,4,6-triméthylphényl)-imidazol-2-ylidène a été testé comme catalyseur de polymérisation du L-lactide, de l'ε caprolactone et du β-butyrolactone, en présence d'un alcool utilisé comme amorceur.In addition, an article from JL Hedrick et al published in 2002, (JACS 124, n ° 6 p 914-915, 2002 ) teaches that N-heterocyclic carbenes can be used as a cyclic ester polymerization catalyst. More specifically, 1,3-bis- (2,4,6-trimethylphenyl) imidazol-2-ylidene has been tested as a catalyst for the polymerization of L-lactide, ε-caprolactone and β-butyrolactone, in the presence of an alcohol used as an initiator.

Un article plus récent et plus complet (cf. JACS 125, n° 10 p 3046-3056, 2003 ) décrit la préparation de carbène in-situ pour éviter les problèmes d'hydrolyse. Les promoteurs utilisés sont de type thiazolium, imidazolium et imidazolinium donnant respectivement des catalyseurs thioazole carbène, imidazole-2-ylidène carbène et imidazolin-2-ylidène carbène, lorsqu'ils sont mis en présence ter-butylate de potassium.A more recent and more complete article (cf. JACS 125, n ° 10 p 3046-3056, 2003 ) describes the carbene preparation in situ to avoid hydrolysis problems. The promoters used are of the thiazolium, imidazolium and imidazolinium type, respectively giving thioazole carbene, imidazol-2-ylidene carbene and imidazolin-2-ylidene carbene catalysts, when they are placed in the presence of potassium tert-butoxide.

La demande de brevet FR-2864543-A divulgue des carbènes obtenus par déprotonation d'un sel d'imidazolium en présence d'une base forte et utilisés pour la synthèse de silicones polyorganosiloxanes, par polymérisation par ouverture de cycle(s) et/ou redistribution de polyorganosiloxanes linéaires ou cycliques.The request for FR-2864543-A discloses carbenes obtained by deprotonation of an imidazolium salt in the presence of a strong base and used for the synthesis of polyorganosiloxane silicones, by ring opening polymerization (s) and / or redistribution of linear or cyclic polyorganosiloxanes.

La demande de brevet FR-2900153-A divulgue un carbène, le dicyclohexyldiaminocarbène obtenu par déprotonation du triflate d'imidazolium correspondant

Figure imgb0002
selon le protocole opératoire suivant:
Figure imgb0003
 The request for FR-2900153-A discloses a carbene, dicyclohexyldiaminocarbene obtained by deprotonation of the corresponding imidazolium triflate
Figure imgb0002
 according to the following operating protocol:
Figure imgb0003

Ce carbène catalyse la polycondensation de silanols du type huile silicone de formule [(CH3)2(OH)SiO1/2]-[(CH3)2SiO2/2]10-[CH3)2(OH)SiO1/2].This carbene catalyzes the polycondensation of silicone oil type silanols of formula [(CH 3 ) 2 (OH) SiO 1/2 ] - [(CH 3 ) 2 SiO 2/2 ] 10 - [CH 3 ) 2 (OH) SiO 1/2 ].

Ces carbènes de type NHC obtenus par déprotonation d'un sel d'imidazolium à l'aide d'une base forte dans un solvant de type THF, sont ensuite isolés par filtration afin d'éliminer le sel formé puis recristallisation, voire sublimation.These NHC carbenes obtained by deprotonation of an imidazolium salt with a strong base in a THF-type solvent, are then isolated by filtration in order to remove the salt formed and then recrystallize, or even sublimate.

A cet égard, le brevet EP-1268440-B1 concerne un procédé de préparation de carbènes N-hétérocycliques comportant le chauffage d'un halogénure de dialkylimidazolium avec une base forte sous pression réduite. Le carbène est distillé pendant sa formation avec un appareil de distillation horizontale, éventuellement distillé avec le même appareil une seconde fois. Il peut être isolé pur sous gaz inerte ou dissout dans un solvant inerte (préférentiellement aromatique).In this respect, the patent EP-1268440-B1 relates to a process for preparing N-heterocyclic carbenes comprising heating a dialkylimidazolium halide with a strong base under reduced pressure. The carbene is distilled during its formation with a horizontal distillation apparatus, possibly distilled with the same apparatus a second time. It can be isolated pure under inert gas or dissolved in an inert solvent (preferably aromatic).

Ce procédé n'est pas industriel car la distillation horizontale qui utilise un appareil de laboratoire n'est possible que pour quelques grammes à quelques dizaines de grammes. De plus, le carbène isolé pur ou en solvant inerte est très sensible à l'oxygène et à la moindre trace d'humidité, et de ce fait a une durée de vie limitée.This process is not industrial because horizontal distillation using a laboratory apparatus is only possible for a few grams to a few tens of grams. In addition, the pure carbene isolated or inert solvent is very sensitive to oxygen and the slightest trace of moisture, and therefore has a limited life.

Ces carbènes sont des espèces très réactives qui se dégradent à l'air libre, ce qui implique de les conserver et de les manipuler sous atmosphère inerte (argon ou azote). Leur synthèse est elle aussi bien évidemment menée sous atmosphère inerte et le solvant utilisé est préalablement séché et fraîchement distillé.These carbenes are very reactive species that degrade in the open air, which involves keeping them and handling them under an inert atmosphere (argon or nitrogen). Their synthesis is also obviously conducted under an inert atmosphere and the solvent used is previously dried and freshly distilled.

L'article de O. Coulembier et al.'Macromolecules 2006, 39, 5617-5628 rapporte l'observation d'un mélange de méthanol, d'un carbène de triazole et d'un méthoxytriazole à 90°C.The article of O. Coulembier et al.'Macromolecules 2006, 39, 5617-5628 reports the observation of a mixture of methanol, a triazole carbene and a methoxytriazole at 90 ° C.

Par ailleurs, l'article de M.A SCHMIDT et al Tetrahedron letters 49 (2008) 4316-4318 divulgue l'interaction de N,N'-bismesitylimidazolium-2-yl et d'alcools, en présence de benzène :

Figure imgb0004
Moreover, the article MA SCHMIDT et al Tetrahedron letters 49 (2008) 4316-4318 discloses the interaction of N, N'-bismsitylimidazolium-2-yl and alcohols in the presence of benzene:
Figure imgb0004

De cette observation, les auteurs déduisent que l'effet stabilisant de ces interactions peut être utilisé pour le stockage de carbènes hétérocycliques azotés, puisque l'élimination des volatils libère ces carbènes hétérocycliques azotés. Dans le cas où l'alcool est le méthanol, cette évaporation des volatils doit s'accompagner d'une désolvatation pour retrouver le complexe carbène-alcool.From this observation, the authors deduce that the stabilizing effect of these interactions can be used for the storage of nitrogenous heterocyclic carbenes, since the elimination of the volatile releases these nitrogenous heterocyclic carbenes. In the case where the alcohol is methanol, this evaporation of the volatiles must be accompanied by a desolvation to find the carbene-alcohol complex.

Eu égard à cet état de la technique, l'invention vise à satisfaire au moins l'un des objectifs essentiels suivants :

  • ∘ perfectionner la synthèse de carbènes, c'est-à-dire la simplifier, la rendre plus économique et aboutir à une forme liquide ou solide, stable et pure qui constitue un système catalytique qui soit facile à stocker et à utiliser et qui soit aussi plus efficace, plus rentable et plus sélectif que les catalyseurs au carbène de l'art antérieur ;
  • ∘ obtenir des carbènes en solution, stables à l'air libre pendant au moins plusieurs mois ;
  • ∘ fournir de nouveaux complexes métalliques de carbène stables, économiques et performants sur le plan catalytique ;
  • ∘ fournir des procédés et des catalyseurs stables, économiques et performants de :
    1. a. préparation de PolyOrganoSiloxanes (POS) par polymérisation par ouverture de cycle et/ou par redistribution-polycondensation de POS
    2. b. hydrosilylation d'au moins un PolyOrganoSiloxane -A- (POS) porteur d'insaturation(s) éthylènique(s) et/ou acétylènique(s), à l'aide d'au moins un polyorganohydrogénosiloxane -B-, ou d'autres composés éthyléniquement et/ou acétyléniquement insaturés
    3. c. hydrogénation
    4. d. métathèse d'oléfines
    5. e. couplage croisé C-C et/ou C-N
    6. f. synthèse énantiosélective
    7. g. synthèse organique
  • ∘ fournir des procédés a à g ayant de meilleurs rendements de conversion ;
  • ∘ fournir un système catalytique à base de carbène performant, qui présente au moins l'une des caractéristiques suivantes :
    • Figure imgb0005
      soluble dans les huiles silicones et en particulier les gommes silicones ;
    • Figure imgb0005
      simple et peu coûteux à synthétiser ;
    • Figure imgb0005
      stable ;
    • Figure imgb0005
      doté d'une bonne tenue à l'hydrolyse ;
    et qui permette :
    • Figure imgb0005
      de polymériser des silicones dans des conditions douces (basses températures ≤ 100°C) ;
    • Figure imgb0005
      de diminuer les temps de réaction en particulier pour la préparation des huiles visqueuses et des gommes ;
    • Figure imgb0005
      de réduire, voire de supprimer, les résidus de catalyseur et de ses dérivés dans le polymère final, afin de préparer des polymères silicone de forte viscosité et de tenue thermique améliorée, et ce de façon rentable ;
    • Figure imgb0005
      de fonctionnaliser toute une palette de POS ;
    • Figure imgb0005
      d'améliorer la polydispersité des polymères formés et de privilégier la formation de structures linéaires par rapport aux oligomères cycliques ;
    • Figure imgb0005
      une élimination aisée des éventuels résidus de catalyseurs ;
    • Figure imgb0005
      de privilégier la formation de polymères silicone linéaires par rapport à la formation de cycliques ;
    • Figure imgb0005
      de garantir une haute reproductibilité ;
    • Figure imgb0005
      et de limiter la sensibilité à la variabilité des matières premières.
In view of this state of the art, the invention aims to satisfy at least one of the following essential objectives:
  • ∘ perfect the synthesis of carbenes, that is to say simplify it, make it more economical and result in a liquid or solid form, stable and pure which is a catalytic system that is easy to store and use and that is also more efficient, more cost-effective and more selective than the carbene catalysts of the prior art;
  • ∘ obtain carbenes in solution, stable in the open air for at least several months;
  • ∘ to provide new stable, economical and catalytically efficient carbene metal complexes;
  • ∘ provide stable, economical and efficient processes and catalysts of:
    1. at. preparation of PolyOrganoSiloxanes (POS) by ring opening polymerization and / or by POS redistribution-polycondensation
    2. b. hydrosilylation of at least one PolyOrganoSiloxane -A- (POS) carrying ethylenic unsaturation (s) and / or acetylenic (s), using at least one polyorganohydrogensiloxane -B-, or other ethylenically and / or acetylenically unsaturated compounds
    3. vs. hydrogenation
    4. d. metathesis of olefins
    5. e. cross coupling CC and / or CN
    6. f. enantioselective synthesis
    7. boy Wut. organic synthesis
  • ∘ provide processes a to g with better conversion efficiencies;
  • ∘ provide a high-efficiency carbene-based catalyst system having at least one of the following characteristics:
    • Figure imgb0005
      soluble in silicone oils and in particular silicone gums;
    • Figure imgb0005
      simple and inexpensive to synthesize;
    • Figure imgb0005
      stable;
    • Figure imgb0005
      with good resistance to hydrolysis;
    and which allows:
    • Figure imgb0005
      to polymerize silicones under mild conditions (low temperatures ≤ 100 ° C);
    • Figure imgb0005
      to reduce the reaction times, in particular for the preparation of viscous oils and gums;
    • Figure imgb0005
      to reduce, or even eliminate, the catalyst residues and its derivatives in the final polymer, in order to prepare silicone polymers of high viscosity and improved thermal resistance, and this in a cost-effective manner;
    • Figure imgb0005
      to functionalize a whole range of POS;
    • Figure imgb0005
      to improve the polydispersity of the polymers formed and to favor the formation of linear structures with respect to cyclic oligomers;
    • Figure imgb0005
      easy removal of any catalyst residues;
    • Figure imgb0005
      to favor the formation of linear silicone polymers with respect to the formation of cyclics;
    • Figure imgb0005
      to guarantee a high reproducibility;
    • Figure imgb0005
      and to limit sensitivity to the variability of raw materials.

Brève description de l'inventionBrief description of the invention

Ces objectifs, parmi d'autres, sont atteints par un procédé de préparation d'un catalyseur ou d'un réactif comprenant un carbène et stable à 20° C se présentant sous la forme d'une solution A constituée d'au moins un alcool et d'au moins un carbène comprenant les étapes suivantes:

  • on fait réagir, de préférence à une température comprise entre 0° C et 100° C, au moins une base forte, éventuellement générée in situ, avec au moins un composé B précurseur d'un carbène C, ledit composé B qui est un sel comprenant une fonction iminium de structure (I) suivante:
    Figure imgb0018
     avec :
    • X étant choisi parmi le groupe constitué par : O, S, -N(R) et -P(R), avec R étant un groupement en C1-C30,
    • R1, R2 et R3 étant des groupements éventuellement substitués, identiques ou différents, en C1-C30 et comprenant éventuellement un ou plusieurs atomes choisi(s) parmi le groupe constitué par: S, P, Si, N et O,
    • X, R1, R2 et R3 pris deux à deux peuvent former un cycle à 5, 6 ou 7 chainons;
    avec comme conditions suivantes :
    • le choix de la base forte s'effectue de manière à pouvoir effectuer une déprotonation de l'hydrogène de la fonction iminium de structure (I), et
    • la réaction s'effectue dans un solvant qui est un alcool ou un mélange d'alcools. Avantageusement, cette déprotonation s'opère à température ambiante (20°C). Il est du mérite des inventeurs d'avoir osé la synthèse de carbène en milieu alcoolique malgré le préjugé existant sur l'incompatibilité carbène-eau ou alcool. Ceci a permis, de manière tout à fait surprenante et inattendue, de s'affranchir de la lourde contrainte de mise en oeuvre d'un milieu réactionnel anhydre et d'isolement du carbène par sublimation avec de très faibles rendement (<40% massique).
These objectives, among others, are achieved by a process for the preparation of a catalyst or a reagent comprising a carbene and stable at 20 ° C. in the form of a solution A consisting of at least one alcohol and at least one carbene comprising the steps of:
  • reacting, preferably at a temperature of between 0 ° C and 100 ° C, at least one strong base, optionally generated in situ, with at least one compound B precursor of a carbene C, said compound B which is a salt comprising an iminium function of structure (I) following:
    Figure imgb0018
     with:
    • X being selected from the group consisting of: O, S, -N (R) and -P (R), with R being a C 1 -C 30 group ,
    • R 1 , R 2 and R 3 being optionally substituted, identical or different, C 1 -C 30 groups and optionally comprising one or more atoms selected from the group consisting of: S, P, Si, N and O ,
    • X, R 1, R 2 and R 3 taken two by two may form a 5-, 6 or 7 membered ring;
    with the following conditions:
    • the choice of the strong base is carried out so as to be able to carry out a deprotonation of the hydrogen of the iminium function of structure (I), and
    • the reaction is carried out in a solvent which is an alcohol or a mixture of alcohols. Advantageously, this deprotonation is carried out at ambient temperature (20 ° C.). It is the merit of the inventors to have dared the synthesis of carbene in an alcoholic medium despite the existing prejudice on the incompatibility carbene-water or alcohol. This has made it possible, quite surprisingly and unexpectedly, to overcome the heavy constraint of using an anhydrous reaction medium and of isolating the carbene by sublimation with very low yield (<40% by mass). .

Le procédé selon l'invention est beaucoup plus simple puisque les opérations de purification sont allégées, voire supprimées. Il est également plus économique. Bref, il est beaucoup plus industriel que les procédés connus. Selon l'invention, le composé B est choisi parmi les composés de formule générale (III) ou (III') suivante :

Figure imgb0019
dans laquelle :

  • A et B représentent indépendamment C ou N, étant entendu que :
    • dans la formule (III), lorsque A représente N, alors T4 n'est pas présent et lorsque B représente N, alors T3 n'est pas présent ;
    • dans la formule (III'), lorsque A représente N, alors T4 ou T4' n'est pas présent et lorsque B représente N, alors T3 ou T3' n'est pas présent ;
  • T3, T3', T4 et T4' représentent indépendamment un atome d'hydrogène; un groupement alkyle ; cycloalkyle éventuellement substitué par un groupe alkyle ou alkoxy ; aryle éventuellement substitué par un groupe alkyle ou alkoxy ; alcényle ; alcynyle ; ou arylalkyle dans lequel la partie aryle est éventuellement substituée par un groupe alkyle ou alkoxy ; ou bien
  • T3 et T4 peuvent former ensemble et avec A et B quand ceux-ci représentent chacun un atome de carbone, un aryle étant entendu que dans ce cas T3' et T4' ne sont pas présents ;
  • T1 et T2 représentent indépendamment un groupement alkyle ; un groupement alkyle éventuellement substitué par un alkyle ; un groupement alkyle perfluoré ou éventuellement substitué par un groupement perfluoroalkyle ; cycloalkyle éventuellement substitué par un groupe alkyle ou alkoxy; aryle éventuellement substitué par un groupe alkyle ou alkoxy ; alcényle ; alcynyle ; ou arylalkyle dans lequel la partie aryle est éventuellement substituée par un groupe alkyle ou alkoxy ; ou bien
  • T1 et T2 représentent indépendamment un radical monovalent de formule (III) suivante :

            -V1-V2     (III)

    dans laquelle :
    • V1 est un groupement divalent hydrocarboné saturé ou non, de préférence un alkylène linéaire ou ramifié en C1-C10, éventuellement substitué,
    • V2 est un groupement monovalent choisi dans le groupe des substituants suivants :
      • ◆ alcoxy, -ORa avec Ra correspondant à hydrogène, alkyle, aryle ;
      • ◆ silyl, -Si(ORb)x(Rc)3-x avec Rb correspondant à hydrogène, alkyle, silyle ou siloxanyle, Rc correspondant à alkyle, aryle et x étant un entier compris entre 0 et 3 ;
      • ◆ amine, de préférence -N(Ra)2 avec Ra correspondant à hydrogène, alkyle, aryle ; ou bien encore ;
  • les substituants T1, T2, T3, T3' T4 et T4' peuvent former deux à deux, lorsqu'ils sont situés sur deux sommets adjacents dans les formules (III) et (III'), une chaîne hydrocarbonée saturée ou insaturée.
  • Z1 représente indépendamment un anion dérivé d'un acide de Brönsted (acide protique) de préférence choisi dans le groupe comprenant :
    • les acides carboxyliques de formule Go-COOH dans laquelle Go représente un alkyle, et avantageusement un alkyle en C1-C22 ; un aryle, avantageusement un aryle en C6-C18 éventuellement substitué par un ou plusieurs alkyle en C1-C6 ;
    • les acides sulfoniques de formule Go-SO3H dans laquelle Go est tel que défini ci-dessus ;
    • les acides phosphoriques de formule Go-PO3H dans laquelle Go est tel que défini ci-dessus ;
    • les acides minéraux suivants : HF, HCl, HBr, HI, H2SO4, H3PO4, HClO4 et HBF4 pris à eux seuls ou en combinaison entre eux ;
    • et leurs mélanges.
The process according to the invention is much simpler since the purification operations are reduced or even eliminated. It is also more economical. In short, it is much more industrial than the known processes. According to the invention, the compound B is chosen from the compounds of the following general formula (III) or (III '):
Figure imgb0019
 in which :
  • A and B independently represent C or N, with the proviso that:
    • in formula (III), when A is N, then T4 is not present and when B is N, then T3 is not present;
    • in formula (III '), when A is N, then T4 or T4' is not present and when B is N, then T3 or T3 'is not present;
  • T3, T3 ', T4 and T4' independently represent a hydrogen atom; an alkyl group; cycloalkyl optionally substituted with an alkyl or alkoxy group; aryl optionally substituted with an alkyl or alkoxy group; alkenyl; alkynyl; or arylalkyl wherein the aryl moiety is optionally substituted with an alkyl or alkoxy group; or
  • T3 and T4 may form together and with A and B when each represents a carbon atom, an aryl being understood that in this case T3 'and T4' are not present;
  • T1 and T2 independently represent an alkyl group; an alkyl group optionally substituted with an alkyl; an alkyl group perfluorinated or optionally substituted by a perfluoroalkyl group; cycloalkyl optionally substituted with an alkyl or alkoxy group; aryl optionally substituted with an alkyl or alkoxy group; alkenyl; alkynyl; or arylalkyl wherein the aryl moiety is optionally substituted with an alkyl or alkoxy group; or
  • T1 and T2 independently represent a monovalent radical of formula (III) below:

    -V1-V2 (III)

    in which :
    • V1 is a saturated or unsaturated divalent hydrocarbon group, preferably an optionally substituted C1-C10 linear or branched alkylene,
    • V2 is a monovalent group selected from the group of the following substituents:
      • Alkoxy, -OR a with R a corresponding to hydrogen, alkyl, aryl;
      • Silyl, -Si (OR b ) x (R c ) 3-x with R b corresponding to hydrogen, alkyl, silyl or siloxanyl, R c corresponding to alkyl, aryl and x being an integer between 0 and 3;
      • Amine, preferably -N (R a ) 2 with R a corresponding to hydrogen, alkyl, aryl; or even ;
  • the substituents T1, T2, T3, T3 'T4 and T4' may form, in pairs, when they are located on two adjacent vertices in formulas (III) and (III '), a saturated or unsaturated hydrocarbon chain.
  • Z1 independently represents an anion derived from a Brönsted acid (protic acid) preferably selected from the group consisting of:
    • carboxylic acids of formula G o -COOH in which G o represents an alkyl, and advantageously a C1-C22 alkyl; aryl, preferably C6-C18 aryl optionally substituted with one or more C1-C6 alkyl;
    • sulphonic acids of formula G o -SO 3 H wherein G o is as defined above;
    • phosphoric acids of formula G o -PO 3 H wherein G o is as defined above;
    • the following mineral acids: HF, HCl, HBr, HI, H 2 SO 4 , H 3 PO 4 , HClO 4 and HBF 4 taken alone or in combination with each other;
    • and their mixtures.

Concernant le sel (III), l'anion Z1 - est l'anion dérivé d'un acide de Brönsted (acide protique) organique ou minéral. Habituellement, l'anion Z1 - est dérivé d'un acide présentant un pKa inférieur à 6. De préférence, Z1 - dérive d'un acide de pKa inférieur à 4, mieux encore inférieur à 2. Les pKa dont il est question ici sont les pKa des acides tels que mesurés dans l'eau.As regards the salt (III), the anion Z 1 - is the anion derived from an organic or inorganic Brönsted acid (protic acid). Usually, the anion Z 1 - is derived from an acid having a pKa of less than 6. Preferably, Z 1 - is derived from an acid of pKa less than 4, more preferably less than 2. The pKa in question here are the pKa acids as measured in water.

Des exemples d'acides sont les acides carboxyliques de formule :

  • Go-COOH, dans laquelle Go représente alkyle, et par exemple (C1-C22)alkyle ; ou bien aryle, et par exemple (C6-C18)aryle éventuellement substitué par un ou plusieurs alkyle, de préférence un ou plusieurs (C1-C6)alkyle ; les acides sulfoniques de formule : Go-SO3H, dans laquelle Go est tel que défini ci-dessus ; et les acides phosphoniques de formule : Go-PO3H dans laquelle Go est tel que défini ci-dessus ; d'autres acides sont HF, HCl, HBr, HI, H2SO4, H3PO4, HClO4 et HBF4.
Examples of acids are the carboxylic acids of formula:
  • G o -COOH, wherein G o represents alkyl, and for example (C1-C22) alkyl; or aryl, and for example (C6-C18) aryl optionally substituted with one or more alkyl, preferably one or more (C1-C6) alkyl; sulfonic acids of formula: G o -SO 3 H, wherein G o is as defined above; and phosphonic acids of formula: G o -PO 3 H wherein G o is as defined above; other acids are HF, HCl, HBr, HI, H 2 SO 4 , H 3 PO 4 , HClO 4 and HBF 4 .

Des exemples préférés d'acides carboxyliques sont l'acide acétique, l'acide benzoïque, et l'acide stéarique. A titre d'acide sulfonique préféré, on citera l'acide benzène sulfonique et à titre d'acide phosphonique préféré, on mentionnera l'acide phénylphosphonique.Preferred examples of carboxylic acids are acetic acid, benzoic acid, and stearic acid. As the preferred sulfonic acid, mention will be made of benzenesulphonic acid and, as the preferred phosphonic acid, mention will be made of phenylphosphonic acid.

Selon l'invention, on préfère plus particulièrement les anions Z1 - dérivés des acides HCl, HI et HBF4 et HPF6.According to the invention, Z 1 - anions derived from HCl, HI and HBF 4 and HPF 6 acids are more particularly preferred.

Ainsi, des anions Z1 - particulièrement préférés, selon l'invention, sont les anions halogénure et le tétrafluoroborate et hexafluorophosphate.
On donne ci-dessous quelques exemples de sels d'imidazolium.

Figure imgb0020
Ces consommables sont soit disponibles dans le commerce, soit facilement préparés par l'homme du métier à partir de composés commerciaux.Thus, especially preferred Z 1 - anions according to the invention are halide anions and tetrafluoroborate and hexafluorophosphate.
Some examples of imidazolium salts are given below.
Figure imgb0020
 These consumables are either commercially available or easily prepared by those skilled in the art from commercial compounds.

Une méthode de synthèse des sels de formule (III) dans laquelle A = B = C est décrite dans US-B-5 077 414 .A method for synthesizing salts of formula (III) in which A = B = C is described in US-B-5,077,414 .

Ce procédé comprend la réaction :

  • ⇒ d'un composé a-dicarbonylé de formule (X) suivante :
    Figure imgb0021
     dans laquelle T3 et T4 sont tels que définis ci-dessus
  • ⇒ avec HCHO et deux amines de formules T1-NH2 et T2-NH2, en présence d'un acide approprié.
This process comprises the reaction:
  • ⇒ an α-dicarbonyl compound of formula (X) below:
    Figure imgb0021
     in which T3 and T4 are as defined above
  • ⇒ with HCHO and two amines of formulas T1-NH 2 and T2-NH 2 , in the presence of a suitable acid.

La nature de l'anion Z1 dans les sels de formule (III) dépend de l'acide utilisé à cette étape. Les acides utilisables sont par exemple ceux énumérés ci-dessus et ceux dont dérive Z1.The nature of the Z1 anion in the salts of formula (III) depends on the acid used in this step. The usable acids are, for example, those listed above and those from which Z1 is derived.

D'autres méthodes de préparation des sels de formule (III) sont proposées dans Chem. Eur. J. 1996, 2, n° 12, pages 1627-1636 et Angew. Chem. Int. Ed. Engl. 1997, 36, 2162-2187 .Other methods for preparing the salts of formula (III) are proposed in Chem. Eur. J. 1996, 2, No. 12, pages 1627-1636 and Angew. Chem. Int. Ed. Engl. 1997, 36, 2162-2187 .

De préférence, l'alcool répond à la formule (I°) R°OH, dans laquelle R° correspond à un groupement alkyle; cycloalkyle; aryle; alcényle; alcynyle; arylalkyle; silyle ou siloxane, R° étant de préférence choisi dans le groupe comprenant : méthyle, éthyle, propyle, butyle. La base forte selon l'invention choisie dans le groupe des hydroxydes, des alcoolates, des hydrures ou des amidures alcalins ou alcalinoterreux, de préférence dans le sous-groupe comprenant : CH3ONa, tertiobutylate de potassium, KOH, NaOH, CH3CH2OMgOCH2CH3 et leurs mélanges.Preferably, the alcohol corresponds to the formula (I °) R ° OH, in which R ° corresponds to an alkyl group; cycloalkyl; aryl; alkenyl; alkynyl; arylalkyl; silyl or siloxane, R ° being preferably selected from the group comprising: methyl, ethyl, propyl, butyl. The strong base according to the invention chosen from the group of hydroxides, alkoxides, hydrides or alkali or alkaline earth metal amides, preferably in the subgroup comprising: CH 3 ONa, potassium tertiobutylate, KOH, NaOH, CH 3 CH 2 OMgOCH 2 CH 3 and mixtures thereof.

Selon une éventualité, cette base forte peut se former in situ, par exemple par ajout de sodium, ou d'hydrure de sodium, ou de magnésium dans l'alcool considéré. C'est ainsi que les alcoolates pouvant être générés in situ. Conformément à l'invention, la déprotonation produit un sel qui précipite et que l'on sépare de la solution A, According to one event, this strong base can be formed in situ, for example by adding sodium, or sodium hydride, or magnesium in the alcohol in question. This is how alcoholates can be generated in situ. According to the invention, the deprotonation produces a salt which precipitates and which is separated from the solution A,

De préférence, le solvant est sublimé de manière à recueillir le carbène C sous forme solide.Preferably, the solvent is sublimed so as to collect the carbene C in solid form.

L'invention concerne aussi une solution A obtenue par le procédé tel que décrit ci-dessus, caractérisée en ce qu'elle est à base d'alcool et d'au moins un carbène C de formule (II) ou (II') :

Figure imgb0022
dans lesquelles :

  • A et B représentent indépendamment C ou N, étant entendu que :
    • dans la formule (II), lorsque A représente N, alors T4 n'est pas présent et lorsque B représente N, alors T3 n'est pas présent ;
    • dans la formule (II'), lorsque A représente N, alors T4 ou T4' n'est pas présent et lorsque B représente N, alors T3 ou T3' n'est pas présent ;
  • T3, T3', T4 et T4' représentent indépendamment un atome d'hydrogène ; un groupement alkyle ; cycloalkyle éventuellement substitué par alkyle ou alkoxy ; aryle éventuellement substitué par alkyle ou alkoxy ; alcényle ; alcynyle ; ou arylalkyle dans lequel la partie aryle est éventuellement substituée par alkyle ou alkoxy ; ou bien
  • T3 et T4 peuvent former ensemble et avec A et B quand ceux-ci représentent chacun un atome de carbone, un aryle étant entendu que dans ce cas T3' et T4' ne sont pas présents ;
  • T1 et T2 représentent indépendamment un groupement alkyle ; un groupement alkyle éventuellement substitué par alkyle; un groupement alkyle perfluoré ou éventuellement substitué par un groupement perfluoroalkyle ; cycloalkyle éventuellement substitué par alkyle ou alkoxy; aryle éventuellement substitué par alkyle ou alkoxy ; alcényle ; alcynyle ; ou arylalkyle dans lequel la partie aryle est éventuellement substituée par alkyle ou alkoxy ; ou bien
  • T1 et T2 représentent indépendamment un radical monovalent de formule (III) suivante :

            -V1-V2     (III)

    dans laquelle :
    • V1 est un groupement divalent hydrocarboné saturé ou non, de préférence un alkylène linéaire ou ramifié en C1-C10, éventuellement substitué,
    • V2 est un groupement monovalent choisi dans le groupe des substituants suivants :
      • ◆ alcoxy, -ORa avec Ra correspondant à hydrogène, alkyle, aryle ;
      • ◆ silyl, -Si(ORb)x(Rc)3-x avec Rb correspondant à hydrogène, alkyle, silyle ou siloxanyle, Rc correspondant à alkyle, aryle et x étant un entier compris entre 0 et 3 ;
      • ◆ amine, de préférence -N(Ra)2 avec Ra correspondant à hydrogène, alkyle, aryle ; ou bien encore ;
  • les substituants T1, T2, T3, T3' T4 et T4' peuvent former deux à deux, lorsqu'ils sont situés sur deux sommets adjacents dans les formules (II) et (II'), une chaîne hydrocarbonée saturée ou insaturée.
The invention also relates to a solution A obtained by the process as described above, characterized in that it is based on alcohol and at least one carbene C of formula (II) or (II '):
Figure imgb0022
 in which :
  • A and B independently represent C or N, with the proviso that:
    • in formula (II), when A is N, then T4 is not present and when B is N, then T3 is not present;
    • in formula (II '), when A is N, then T4 or T4' is not present and when B is N, then T3 or T3 'is not present;
  • T3, T3 ', T4 and T4' independently represent a hydrogen atom; an alkyl group; cycloalkyl optionally substituted with alkyl or alkoxy; aryl optionally substituted with alkyl or alkoxy; alkenyl; alkynyl; or arylalkyl wherein the aryl moiety is optionally substituted with alkyl or alkoxy; or
  • T3 and T4 may form together and with A and B when each represents a carbon atom, an aryl being understood that in this case T3 'and T4' are not present;
  • T1 and T2 independently represent an alkyl group; an alkyl group optionally substituted with alkyl; an alkyl group perfluorinated or optionally substituted by a perfluoroalkyl group; cycloalkyl optionally substituted with alkyl or alkoxy; aryl optionally substituted with alkyl or alkoxy; alkenyl; alkynyl; or arylalkyl wherein the aryl moiety is optionally substituted with alkyl or alkoxy; or
  • T1 and T2 independently represent a monovalent radical of formula (III) below:

    -V1-V2 (III)

    in which :
    • V1 is a saturated or unsaturated divalent hydrocarbon group, preferably an optionally substituted C1-C10 linear or branched alkylene,
    • V2 is a monovalent group selected from the group of the following substituents:
      • Alkoxy, -OR a with R a corresponding to hydrogen, alkyl, aryl;
      • Silyl, -Si (OR b ) x (R c ) 3-x with R b corresponding to hydrogen, alkyl, silyl or siloxanyl, R c corresponding to alkyl, aryl and x being an integer between 0 and 3;
      • Amine, preferably -N (R a ) 2 with R a corresponding to hydrogen, alkyl, aryl; or even ;
  • the substituents T1, T2, T3, T3 'T4 and T4' may form, in pairs, when they are located on two adjacent vertices in formulas (II) and (II '), a saturated or unsaturated hydrocarbon chain.

Par alkyle, on désigne une chaîne hydrocarbonée saturée, linéaire ou ramifiée, éventuellement substituée (e.g. par un ou plusieurs alkyles), de préférence de 1 à 10 atomes de carbone, par exemple de 1 à 8 atomes de carbone, mieux encore de 1 à 7 atomes de carbone.Alkyl means a linear or branched saturated hydrocarbon-based chain, optionally substituted (eg with one or more alkyls), preferably from 1 to 10 carbon atoms, for example from 1 to 8 carbon atoms, more preferably from 1 to 7 carbon atoms.

Des exemples de groupements alkyle sont notamment méthyle, éthyle, isopropyle, n-propyle, tert-butyle, isobutyle, n-butyle, n-pentyle, isoamyle et 1,1-diméthylpropyle.
La partie alkyle du groupement alcoxy est telle que définie ci-dessus.
Le groupement alkyle perfluoré ou éventuellement substitué par un groupement perfluoroalkyle correspond, de préférence, à la formule :

        -(CH2)p-CqF2q+1

dans laquelle p représente 0, 1, 2, 3 ou 4; q est un entier de 1 à 10 ; et CqF2q+1 est linéaire ou ramifié. Des exemples préférés de ce groupement sont : -(CH2)2-(CF2)5-CF3 et -(CF2)7-CF3.Examples of alkyl groups are in particular methyl, ethyl, isopropyl, n-propyl, tert-butyl, isobutyl, n-butyl, n-pentyl, isoamyl and 1,1-dimethylpropyl.
The alkyl part of the alkoxy group is as defined above.
The perfluoroalkyl group or optionally substituted by a perfluoroalkyl group preferably corresponds to the formula:

- (CH 2 ) p -C q F 2q + 1

wherein p is 0, 1, 2, 3 or 4; q is an integer of 1 to 10; and C q F 2q + 1 is linear or branched. Preferred examples of this group are: - (CH 2 ) 2 - (CF 2 ) 5 -CF 3 and - (CF 2 ) 7 -CF 3 .

L'expression aryle désigne un groupement hydrocarboné aromatique, ayant de 6 à 18 atomes de carbone, monocyclique ou polycyclique et de préférence monocyclique ou bicyclique. Il doit être entendu que, dans le cadre de l'invention, par groupement aromatique polycyclique, on entend un groupement présentant deux ou plusieurs noyaux aromatiques, condensés (orthocondensés ou ortho et péricondensés) les uns aux autres, c'est-à-dire présentant, deux à deux, au moins deux carbones en commun.
Ledit groupement hydrocarboné aromatique ("aryle") est éventuellement substitué par exemple par un ou plusieurs alkyles en C1-C3, un ou plusieurs groupements hydrocarbonés halogénés (e.g. CF3), un ou plusieurs alcoxy (e.g. CH3O) ou un ou plusieurs groupements hydrocarbonés comprenant un ou plusieurs motifs cétone (e.g. CH3CO-).
A titre d'exemple d'aryle, on peut mentionner les radicaux phényle, naphtyle, anthryle et phénanthryle.The term "aryl" denotes an aromatic hydrocarbon group having from 6 to 18 carbon atoms, monocyclic or polycyclic and preferably monocyclic or bicyclic. It should be understood that, in the context of the invention, a polycyclic aromatic group means a group having two or more aromatic rings condensed (orthocondensed or ortho and peri-condensed) to each other, that is to say presenting, two by two, at least two carbons in common.
Said aromatic hydrocarbon group ("aryl") is optionally substituted for example by one or more C1-C3 alkyls, one or more halogenated hydrocarbon groups (eg CF 3 ), one or more alkoxy (eg CH 3 O) or one or more hydrocarbon groups comprising one or more ketone units (eg CH 3 CO-).
As an example of aryl, mention may be made of phenyl, naphthyl, anthryl and phenanthryl radicals.

L'expression arylalkyle désigne un groupement alkyle tel que défini ci-dessus, substitué par un ou plusieurs groupements aryle sur sa chaîne hydrocarbonée, le groupement aryle étant tel que défini ci-dessus. Des exemples en sont benzyle et triphénylméthyle.The term arylalkyl denotes an alkyl group as defined above, substituted with one or more aryl groups on its hydrocarbon chain, the aryl group being as defined above. Examples are benzyl and triphenylmethyl.

Par cycloalkyle, on entend un groupement hydrocarboné saturé mono- ou polycyclique, de préférence mono- ou bicyclique, présentant préférablement de 3 à 10 atomes de carbone, mieux encore de 3 à 8. Par groupement hydrocarboné saturé polycyclique, on entend un groupement présentant deux ou plusieurs noyaux cycliques rattachés les uns aux autres par des liaisons σ ou/et condensés deux à deux.
Des exemples de groupements cycloalkyle polycycliques sont adamantane et norbornane. Des exemples de groupements cycloalkyle monocycliques sont cyclopropyle, cyclobutyle, cyclopentyle, cyclohexyle, cycloheptyle et cyclooctyle.Cycloalkyl means a mono- or polycyclic saturated hydrocarbon group, preferably mono- or bicyclic, preferably having from 3 to 10 carbon atoms, more preferably from 3 to 8. Polycyclic saturated hydrocarbon group means a group having two or more cyclic rings attached to each other by σ or / and fused two by two.
Examples of polycyclic cycloalkyl groups are adamantane and norbornane. Examples of monocyclic cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

Par alcényle, on entend une chaîne hydrocarbonée insaturée, linéaire ou ramifiée, substituée ou non, présentant au moins une double liaison oléfinique, et plus préférablement une seule double liaison. De préférence, le groupement alcényle présente de 2 à 8 atomes de carbone, mieux encore de 2 à 6. Cette chaîne hydrocarbonée comprend éventuellement au moins un hétéroatome tel que O, N, S.
Des exemples préférés de groupements alcényle sont les groupements allyle et homoallyle. Par alcynyle, on entend selon l'invention, une chaîne hydrocarbonée insaturée, linéaire ou ramifiée, substituée ou non, présentant au moins une triple liaison acétylénique, et plus préférablement une seule triple liaison. De préference, le groupement alcynyle présente de 2 à 8 atomes de carbone, mieux encore de 2 à 6 atomes de carbone. A titre d'exemple, on peut citer le groupement acétylényle, ainsi que le groupement propargyle. Cette chaîne hydrocarbonée comprend éventuellement au moins un hétéroatome tel que O, N, S.By alkenyl is meant a linear or branched unsaturated hydrocarbon chain, substituted or unsubstituted, having at least one olefinic double bond, and more preferably a single double bond. Preferably, the alkenyl group has from 2 to 8 carbon atoms, more preferably from 2 to 6. This hydrocarbon chain optionally comprises at least one heteroatom such as O, N, S.
Preferred examples of alkenyl groups are allyl and homoallyl groups. By alkynyl is meant according to the invention, a unsaturated hydrocarbon chain, linear or branched, substituted or unsubstituted, having at least one acetylenic triple bond, and more preferably a single triple bond. Preferably, the alkynyl group has from 2 to 8 carbon atoms, more preferably from 2 to 6 carbon atoms. By way of example, mention may be made of the acetylenyl group and the propargyl group. This hydrocarbon-based chain optionally comprises at least one heteroatom such as O, N, S.

Par silyle, on entend selon l'invention, un groupement linéaire ou ramifié contenant au moins un atome de silicium. Les chaînes polydiméthylsiloxane sont des exemples de groupements silyle.By silyl is meant according to the invention, a linear or branched group containing at least one silicon atom. Polydimethylsiloxane chains are examples of silyl groups.

Les carbènes de formule (II) et (II') peuvent présenter au moins deux noyaux condensés, c'est-à-dire que deux groupements au moins parmi T1, T2, T3, T3', T4 et T4' situés sur deux sommets adjacents, forment ensemble une chaîne hydrocarbonée saturée ou insaturée, présentant de préférence de 3 à 6 atomes de carbones. Par chaîne hydrocarbonée saturée ou insaturée, on entend une chaîne hydrocarbonée linéaire ou ramifiée pouvant présenter ou non une ou plusieurs insaturations de type double liaison oléfinique ou triple liaison acétylénique.The carbenes of formula ( II ) and ( II ' ) may have at least two fused rings, that is to say that at least two groups of T1, T2, T3, T3', T4 and T4 'situated on two vertices adjacent, together form a saturated or unsaturated hydrocarbon chain, preferably having from 3 to 6 carbon atoms. The term "saturated or unsaturated hydrocarbon-based chain" means a linear or branched hydrocarbon-based chain which may or may not have one or more olefinic double bond or acetylenic triple bond unsaturations.

Concernant les formes préférées de réalisation dans les formules (II) ou (II'), ce sont des formes dans lesquelles A = B = atome de carbone dans la formule (II) donnée supra.Concerning the preferred embodiments in the formulas (II) or (II '), they are forms in which A = B = carbon atom in the formula (II) given above.

Des significations préférées pour T1 et T2 dans cette formule (II) sont :

  • alkyle, en particulier n-propyle, n-pentyle, néo-pentyle (-CH2-C(CH3)3) ;
  • cycloalkyle, en particulier cyclopentyle, cyclohexyle ou adamantyle ;
  • alcényle, en particulier allyle (-CH2-CH=CH2), méthallyle (-CH2-C(CH3)=CH2) ;
  • alcynyle, en particulier propargyle, homopropargyle (-(CH2)2-C≡CH) ;
  • ou groupement monovalent (V) défini supra, en particulier :
    Figure imgb0023
Preferred meanings for T1 and T2 in this formula (II) are:
  • alkyl, in particular n-propyl, n-pentyl, neo-pentyl (-CH 2 -C (CH 3 ) 3 );
  • cycloalkyl, in particular cyclopentyl, cyclohexyl or adamantyl;
  • alkenyl, in particular allyl (-CH 2 -CH = CH 2 ), methallyl (-CH 2 -C (CH 3 ) = CH 2 );
  • alkynyl, especially propargyl, homopropargyl (- (CH 2 ) 2 -C≡CH);
  • or monovalent group (V) defined above, in particular:
    Figure imgb0023

Toujours dans la formule (II) et de préférence, T3 et T4 correspondent tous deux à l'hydrogène ou forment ensemble un aryle, et mieux encore un phényle.Still in formula ( II ) and preferably, T3 and T4 are both hydrogen or together form aryl, and more preferably phenyl.

A titre d'exemples de carbènes, on peut citer ceux décrits dans le tableau 2, page 48 de la publication " Bourissou et al. Chem. Rev. 2000, 100, 39-91 ".As examples of carbenes, mention may be made of those described in Table 2, page 48 of the publication " Bourissou et al. Chem. Rev. 2000, 100, 39-91 ".

Conformément à l'invention, le (ou les) carbène(s) :

  • est (sont) préparé(s) séparément,
  • et/ou est (sont) généré(s) in-situ à partir d'au moins un précurseur.
According to the invention, the carbene (s):
  • is (are) prepared separately,
  • and / or is (are) generated in-situ from at least one precursor.

La nouvelle forme liquide ou solide de carbèneThe new liquid or solid form of carbene

Le procédé selon l'invention donne donc accès à une solution à base d'alcool et de carbène. De manière surprenante et inattendue, cette solution alcoolique est stable et catalytique.The method according to the invention thus gives access to a solution based on alcohol and carbene. Surprisingly and unexpectedly, this alcoholic solution is stable and catalytic.

L'invention couvre également cette solution alcoolique stable et catalytique de carbène per se, obtenue par le procédé selon l'invention.The invention also covers this stable and catalytic carbene per se alcoholic solution obtained by the process according to the invention.

Les applicationsApplications

Suivant un autre de ses aspects, le présent exposé vise un procédé de préparation de PolyOrganoSiloxanes (POS) par polymérisation par ouverture de cycle et/ou par redistribution de POS et/ou par polycondensation, en présence d'un catalyseur (C) comprenant au moins un carbène tel qu'obtenu par le procédé tel que défini supra, ledit carbène se présentant sous la forme d'une solution alcoolique ou d'un solide extrait dudit liquide.According to another of its aspects, the present disclosure relates to a process for the preparation of Polyorganosiloxanes (POS) by ring opening polymerization and / or by POS redistribution and / or by polycondensation, in the presence of a catalyst (C) comprising at least one less a carbene as obtained by the process as defined above, said carbene being in the form of an alcoholic solution or a solid extracted from said liquid.

Au sens du présent exposé, la "polymérisation par ouverture de cycle(s)" correspond à une polymérisation dans laquelle un composé cyclique (monomère) est ouvert pour former un polymère linéaire.As used herein, "ring opening polymerization (s)" refers to a polymerization in which a cyclic compound (monomer) is opened to form a linear polymer.

Au sens du présent exposé, la "polymérisation par redistribution" correspond à l'acception de l'homme du métier dans la chimie des silicones. En particulier, la "polymérisation par redistribution" s'entend dans le domaine des silicones, comme un réarrangement d'organosiloxanes de structures et/ou de masse molaire différentes. Ce réarrangement conduit à un seul nouveau POS.For the purposes of this disclosure, "redistribution polymerization" corresponds to the meaning of a person skilled in the art of silicone chemistry. In particular, the "redistribution polymerization" is understood in the field of silicones, as a rearrangement of organosiloxanes of different structures and / or molecular weight. This rearrangement leads to a single new POS.

L'invention ouvre de nouvelles voies dans la catalyse de :

  • la préparation de PolyOrganoSiloxanes (POS) par polymérisation par ouverture de cycle et/ou par redistribution et/ou polycondensation de POS;
  • l'hydrosilylation d'au moins un PolyOrganoSiloxane -A- (POS) porteur d'insaturation(s) éthylènique(s) et/ou acétylènique(s), à l'aide d'au moins un polyorganohydrogénosiloxane -B-, ou d'autres composés éthyléniquement et/ou acétyléniquement insaturés ;
  • l'hydrogénation ;
  • la métathèse d'oléfines ;
  • le couplage croisé C-C et/ou C-N ;
  • la synthèse asymétrique ou énantiosélective ;
  • ou la synthèse organique : réactions d'estérification, trans-estérification ; condensation de type aldolisation, par exemple.
The invention opens new ways in the catalysis of:
  • the preparation of Polyorganosiloxanes (POS) by ring opening polymerization and / or by redistribution and / or polycondensation of POS;
  • hydrosilylation of at least one polyorganosiloxane -A- (POS) bearing ethylenic (s) unsaturation (s) and / or acetylenic (s), using at least one polyorganohydrogensiloxane -B-, or other ethylenically and / or acetylenically unsaturated compounds;
  • hydrogenation;
  • metathesis of olefins;
  • cross coupling CC and / or CN;
  • asymmetric or enantioselective synthesis;
  • or organic synthesis: esterification, trans-esterification reactions; aldol condensation type, for example.

Ces voies sont performantes en termes de stockage et de manipulation de facilité de mise en oeuvre du catalyseur au carbène et en termes d'activité catalytique, de sélectivité (meilleurs taux de transformation et rendement), de facilité de mise en oeuvre (basse température, pas ou peu de purification), d'obtention de POS ayant de bons indices de polymolécularité et pouvant avoir de fortes viscosités, entre autres.These routes are efficient in terms of storage and handling ease of implementation of the catalyst to carbene and in terms of catalytic activity, selectivity (better conversion rates and yield), ease of implementation (low temperature, no or little purification), obtaining POS having good polymolecularity indices and can have high viscosities, among others.

Ces performances sont d'autant plus intéressantes qu'elles se doublent d'avantages en termes de coût, de sécurité et de non écotoxicité, notamment.These performances are all the more interesting because they are accompanied by advantages in terms of cost, safety and non-ecotoxicity, among others.

Les exemples qui suivent permettront de mieux appréhender le procédé et le carbène liquide ou solide selon l'invention, en faisant ressortir tous leurs avantages et les variantes possibles de mises en oeuvre.The following examples will better understand the process and the liquid or solid carbene according to the invention, highlighting all their advantages and possible variants of implementations.

EXEMPLESEXAMPLES Généralités : Generalities

Dans le protocole suivant l'invention, on utilise directement un alcool comme solvant de la réaction, permettant la protection instantanée du carbène dès sa formation. La synthèse est réalisée à l'air libre.

Figure imgb0024
In the protocol according to the invention, an alcohol is used directly as solvent for the reaction, allowing instantaneous protection of the carbene as soon as it is formed. The synthesis is carried out in the open air.
Figure imgb0024

Cette synthèse d'un NHC (R1: tert-butyle) a été testée dans plusieurs conditions par variation de la base et de l'alcool utilisés. Il en ressort que l'utilisation d'un solvant de type éthanol ou isopropanol et d'une base de type tBuOK ou KOH permettent l'obtention du carbène. En effet les spectres RMN (proton et carbone) des solutions sont identiques à ceux obtenus dans le cas d'un mélange, de carbène pur et d'alcool.This synthesis of an NHC (R 1 : tert-butyl) was tested under several conditions by variation of the base and the alcohol used. It follows that the use of a solvent of the ethanol or isopropanol type and a tBuOK or KOH type base make it possible to obtain the carbene. Indeed, the NMR spectra (proton and carbon) of the solutions are identical to those obtained in the case of a mixture, pure carbene and alcohol.

Les éléments permettant d'attester la formation du carbène sont notamment :

  • L'absence de proton sur le carbone situé entre les deux atomes d'azote (spectre RMN 1H)
  • La présence d'un signal à 130 ppm correspondant à un carbone de type quaternaire (spectre RMN 13C)
The elements allowing to attest the formation of the carbene are in particular:
  • The absence of a proton on the carbon located between the two nitrogen atoms ( 1 H NMR spectrum)
  • The presence of a 130 ppm signal corresponding to a quaternary carbon ( 13 C NMR spectrum)

Le procédé selon l'invention a ainsi permis de synthétiser un nouveau carbène, habituellement trop instable pour être isolé (R1: méthyle).The method according to the invention thus made it possible to synthesize a new carbene, usually too unstable to be isolated (R 1 : methyl).

-A- Synthèse-A- Synthesis Exemple A1 : Synthèse du NHC-tBu par déprotonation avec tBuOK dans l'isopropanol Example A1 Synthesis of NHC-tBu by deprotonation with tBuOK in isopropanol

On pèse 210 mg de tBuOK (1,87 mmole) auxquels on rajoute à l'air libre une solution de 500 mg de sel d'imidazolium (1,87 mmole) dans environ 4 mL d'isopropanol sous agitation. On observe une légère exothermie dans les premières minutes. Après environ 1h d'agitation à température ambiante on élimine KCl par filtration sur fritté et on obtient une solution légèrement colorée.210 mg of tBuOK (1.87 mmol) are weighed and a solution of 500 mg of imidazolium salt (1.87 mmol) in about 4 ml of isopropanol with stirring is added to the air. A slight exotherm is observed in the first minutes. After stirring for approximately one hour at room temperature, KCl is removed by sinter filtration and a slightly colored solution is obtained.

Les spectres RMN (proton et carbone) de cette solution sont représentés ci-dessous.The NMR spectra (proton and carbon) of this solution are shown below.

Exemple A2 : Synthèse du NHC-tBu par déprotonation avec KOH dans l'isopropanol Example A2 Synthesis of NHC-tBu by Deprotonation with KOH in Isopropanol

On pèse 93 mg de KOH en pastille (1,66 mmole) que l'on dissout dans 2 mL d'isopropanol, en rajoutant quelques gouttes d'eau distillée afin de bien dissoudre. On rajoute ensuite 450 mg de sel d'imidazolium (1,66 mmole) dissouts dans 2 mL d'isopropanol. On observe une légère exothermie dans les premières minutes. Après environ 1h d'agitation à température ambiante on filtre sur fritté et on obtient une solution légèrement colorée.

Figure imgb0025
93 mg of KOH in pellet (1.66 mmol) are weighed and dissolved in 2 ml of isopropanol, adding a few drops of distilled water in order to dissolve well. 450 mg of imidazolium salt (1.66 mmol) dissolved in 2 ml of isopropanol are then added. A slight exotherm is observed in the first minutes. After stirring for approximately one hour at room temperature, the mixture is sintered and a slightly colored solution is obtained.
Figure imgb0025

Spectre 1 : RMN 1H et 13C (synthèse du NHC-tBu, base : tBuOK, solvant : iPrOH)Spectrum 1: 1 H NMR and 13 C (synthesis of NHC-tBu, base: tBuOK, solvent: iPrOH)

RMN 1H 1 H NMR RMN 13C (jmod)NMR 13 C (jmod) 1.15 (iPrOH)1.15 (iPrOH) 25.3 (iPrOH)25.3 (iPrOH) 1.21 (tBuOH)1.21 (tBuOH) 30.0 (N-C-(CH3)3)30.0 (NC- ( C H 3 ) 3 ) 1.47 (s, 18H, N-C-(CH 3)3)1.47 (s, 18H, NC- (C H 3 ) 3 ) 31.2 (tBuOH)31.2 (tBuOH) 3.95 (iPrOH)3.95 (iPrOH) 60.6 (N-C-(CH3)3)60.6 (N- C - (CH 3 ) 3 ) 4.81 (iPrOH)4.81 (iPrOH) 63.2 (iPrOH)63.2 (iPrOH) 7.15 (C6D6)7.15 (C 6 D 6 ) 68.4 (tBuOH)68.4 (tBuOH) 7.54 (s, 2H, N-CH=CH-N)7.54 (s, 2H, NC H = C H -N) 121.4 (N-CH=CH-N)121.4 (N- C H = C H-N) 132.8 (C carbénique)132.8 (carbene C)

Exemple A3 : Préparation d'une solution éthanolique du carbène NHC-Cy2 (Cy = cyclohexyl) :Example A3: Preparation of an ethanolic solution of carbene NHC-Cy2 (Cy = cyclohexyl)

Figure imgb0026
Figure imgb0026

Dans un ballon de 50 ml contenant 4 g de tétrafluoroborate de N,N'-dicyclohexylimidazolium (12.5 mmol) et 1.4 g de tertiobutylate de potassium (12.5 mmol) refroidis à 0°C est ajouté 20 ml d'éthanol. Après 10 min, le mélange hétérogène est agité à 20°C pendant une à deux heures. Le solide (KBF4) est alors filtré, puis rincé par 6 ml d'éthanol. Le filtrat limpide légèrement jaune est concentré pour donner une solution de carbène à 43.87 %p théorique, utilisée telle quelle comme catalyseur ou complexant. Il est préférable de conserver cette solution à température ambiante (20°C), le carbène pouvant cristalliser à froid. Un gaz inerte n'est pas nécessaire.In a 50 ml flask containing 4 g of N, N'-dicyclohexylimidazolium tetrafluoroborate (12.5 mmol) and 1.4 g of potassium tert-butoxide (12.5 mmol) cooled at 0 ° C., 20 ml of ethanol are added. After 10 min, the heterogeneous mixture is stirred at 20 ° C for one to two hours. The solid (KBF4) is then filtered and rinsed with 6 ml of ethanol. The clear, slightly yellow filtrate is concentrated to give a 43.87% theoretical carbene solution, used as such as catalyst or complexing agent. It is best to keep this solution at room temperature (20 ° C), the carbene can crystallize cold. An inert gas is not necessary.

-B- Réactivité-B- Reactivity B1 Catalyseurs d'hydrosilylation : platine-carbèneB1 Hydrosilylation catalysts: platinum-carbene B11 Synthèse de « platine-carbène » :B11 Synthesis of platinum-carbene: Réaction générale :General reaction:

Figure imgb0027
Figure imgb0027

Exemple B111 : Synthèse à partir de tétrafluoroborate de dicyclohexylimidazolium (WO 02/98888 du 4 juin 2002) → échantillon 1 Example B111 : Synthesis from dicyclohexylimidazolium tetrafluoroborate (WO 02/98888 of June 4, 2002) → sample 1

La synthèse nécessite un réacteur sous gaz inerte, du THF anhydre, du toluène pour précipiter la majeure partie du sel de potassium, 2 filtrations ; la productivité est faible (13 % p/p), le rendement moyen (87%) et le produit isolé contient le plus souvent des sels (dosage Pt = 30.4 %p pour une théorie de 31.8 %p).The synthesis requires a reactor under inert gas, anhydrous THF, toluene to precipitate most of the potassium salt, 2 filtrations; the productivity is low (13% w / w), the average yield (87%) and the isolated product most often contains salts (Pt assay = 30.4% p for a theory of 31.8% p).

Exemple B112 : Synthèse en milieu dilué THF selon l'invention (dilution égale à 1)) -→ échantillon 2 Example B112 : Synthesis in THF diluted medium according to the invention (dilution equal to 1) - → sample 2

Dans un ballon monocol de 50 ml sont placés 10 g de platine de Karsted à 10.25 %p de platine (5.25 mmol) et 10 ml de THF. A la solution obtenue est ajouté sous agitation 3.06 g de la solution de carbène NHC-Cy2 décrite en A3 (5.78 mmol). Après 2h à 20°C, la solution est évaporée, le solide gras est repris par 20 ml d'isopropanol, la suspension est filtrée et le solide est séché sous vide : 2.8 g obtenus soit 87.5 % de rendement.
Anal. élém. : 31.01 % Pt
→ rendement non optimisé égal, produit plus pur, procédé très simplifié.In a 50 ml monocolumn flask are placed 10 g of 10.25% platinum Karsted platinum (5.25 mmol) and 10 ml of THF. To the resulting solution is added with stirring 3.06 g of the NHC-Cy2 carbene solution described in A3 (5.78 mmol). After 2h at 20 ° C, the solution is evaporated, the fatty solid is taken up in 20 ml of isopropanol, the suspension is filtered and the solid is dried under vacuum: 2.8 g obtained is 87.5% yield.
Anal. comp. : 31.01% Pt
→ unrivaled efficiency equal, product more pure, very simplified process.

Exemple B113 : Synthèse sans solvant → échantillon 3 Example B113 : Synthesis without solvent → sample 3

Même mode opératoire que ci-dessus sans THF : ajout de la solution de carbène sur le platine de Karsted, précipitation après 10 min d'agitation. Après 2h, 20 ml d'isopropanol sont ajouté. Le solide blanc est filtré, rincé par 5 ml du même solvant et séché sous vide : 2.75 g obtenus soit rendement 86 %.
Anal. élém. : 31.43 % Pt
→ rendement non optimisé égal, produit encore plus pur, procédé encore simplifié.Same procedure as above without THF: addition of the carbene solution on the Karsted platinum, precipitation after stirring for 10 minutes. After 2h, 20 ml of isopropanol are added. The white solid is filtered, rinsed with 5 ml of the same solvent and dried under vacuum: 2.75 g obtained is 86% yield.
Anal. comp. : 31.43% Pt
→ unrivaled efficiency equal, product even purer, process still simplified.

Exemple B114 : Même réaction que B112 (avec THF) avec une solution de carbène préparée un mois auparavant et stockée sans précaution à 20°C → échantillon 4Example B114: Same reaction as B112 (with THF) with a carbene solution prepared a month ago and stored without precaution at 20 ° C → sample 4

2.8 g obtenus soit 87.5 % de rendement.
Anal. élém. : 31.51 %Pt
→ rendement non optimisé égal, produit encore plus pur, procédé robuste et simple.2.8 g achieved either 87.5% yield.
Anal. comp. : 31.51% Pt
→ unrivaled efficiency equal, product even more pure, robust and simple process.

Exemple B115 : Préparation du platine carbène avec carbène = NHC-tBu2 :Example B115: Preparation of platinum carbene with carbene = NHC-tBu2:

Même mode opératoire que dans l'exemple B112, avec une solution éthanolique de carbène NHC-tBu2 à 37.8 %p (2.76 g pour 5.78 mmol). Obtention de 2.6 g d'un solide blanc fin soit rendement 88 %. Anal. élém. : 34.56 % Pt (th. 34.73 %)Same procedure as in Example B112, with an ethanolic solution of carbene NHC-tBu2 at 37.8% p (2.76 g for 5.78 mmol). Obtaining 2.6 g of a fine white solid is yield 88%. Anal. comp. : 34.56% Pt (Th.34.73%)

Exemple B12 : Tests des catalyseursExample B12: Catalyst Tests

La réaction étudiée est l'hydrosilylation du 1-octène par le 1,1,1,2,3,3,3-heptaméthyltrisiloxane sans solvant :

Figure imgb0028
The reaction studied is the hydrosilylation of 1-octene by 1,1,1,2,3,3,3-heptamethyltrisiloxane without solvent:
Figure imgb0028

Dans un ballon tricol de 50 ml sont placés 10 g d'octène (89.1 mmol, 1.2 éq). Le ballon est chauffé à 85°C en consigne. 27 µl de solution de platine carbène à 2.7 % dans le xylène (1.1 x 10-3 mol%/octène) sont ajoutés et l'hydrosiloxane est ajouté à l'aide d'un pousse seringue sur 1h30. La disparition de l'hydrosiloxane est suivie au cours du temps par gazométrie. Les résultats de conversion de l'hydrosilane sont donnés dans le tableau ci-dessous : Pt-carbène conversion SiH à 20% de coulée conversion SiH à 50% de coulée conversion SiH à 100% de coulée 1h30 après fin coulée échantillon 1 11,0% 76,0% 90,0% 99,7% échantillon 2 8,3% 70,0% 91,0% 99,5% échantillon 3 10,0% 75,0% 92,0% 99,7% échantillon 4 16,7% 78,0% 91,0% 99,8% In a three-necked flask of 50 ml are placed 10 g of octene (89.1 mmol, 1.2 eq). The flask is heated to 85 ° C as a deposit. 27 μl of 2.7% platinum carbene solution in xylene (1.1 × 10 -3 mol% / octene) are added and the hydrosiloxane is added using a syringe pump over 1h30. The disappearance of the hydrosiloxane is monitored over time by gasometry. The conversion results of the hydrosilane are given in the table below: Pt-carbene SiH conversion at 20% casting SiH conversion at 50% casting SiH conversion at 100% casting 1h30 after end casting sample 1 11.0% 76.0% 90.0% 99.7% sample 2 8.3% 70.0% 91.0% 99.5% sample 3 10.0% 75.0% 92.0% 99.7% sample 4 16.7% 78.0% 91.0% 99.8%

On en déduit que tous les catalyseurs sont globalement équivalents.It is deduced that all the catalysts are globally equivalent.

Exemple B13 :Example B13:

On évalue la stabilité en solution d'un carbène NHC di tertiobutyl (NHC-tBu2, préparé à l'Exemple B115) :

  1. a) Comparatif, dans le THF et sous atmosphère d'air ambiant après :
    • 3h : 0% de dégradation,
    • 20h : 2% de dégradation,
    • 48h: 25% de dégradation,
      • 7 jours : 100% de dégradation
  2. b) Invention, en solution (40% poids) dans MeOH, EtOH ou iPrOH :
    • après 1 an aucune dégradation
The solution stability of an NHC di tertiarybutyl carbene (NHC-tBu2, prepared in Example B115) is evaluated:
  1. a) Comparative, in THF and under ambient air atmosphere after:
    • 3h: 0% degradation,
    • 20h: 2% degradation,
    • 48h: 25% degradation,
      • 7 days: 100% degradation
  2. b) Invention, in solution (40% by weight) in MeOH, EtOH or iPrOH:
    • after 1 year no degradation

Claims (3)

  1. Process for the preparation of a catalyst or of a reactant comprising a carbene and stable at 20°C which is provided in the form of a stable alcoholic solution A composed of at least one alcohol and at least one carbene comprising the following stages:
    - at least one strong base, optionally generated in situ, is reacted, in a solvent which is an alcohol or a mixture of alcohols, with at least one compound B which is the precursor of a carbene C, said compound B, which is a salt comprising an iminium functional group, is chosen from the compounds of following general formula (III) or (III'):
    Figure imgb0033
     in which:
    - A and B independently represent C or N, it being understood that:
    • in the formula (III), when A represents N, then T4 is not present and, when B represents N, then T3 is not present;
    • in the formula (III'), when A represents N, then T4 or T4' is not present and, when B represents N, then T3 or T3' is not present;
    - T3, T3', T4 and T4' independently represent a hydrogen atom; an alkyl group; a cycloalkyl group optionally substituted by an alkyl or alkoxy group; an aryl group optionally substituted by an alkyl or alkoxy group; an alkenyl group; an alkynyl group; or an arylalkyl group in which the aryl part is optionally substituted by an alkyl or alkoxy group; or else
    - T3 and T4 can form, together and with A and B when the latter each represent a carbon atom, an aryl, it being understood that, in this case, T3' and T4' are not present;
    - T1 and T2 independently represent an alkyl group; an alkyl group optionally substituted by an alkyl; an alkyl group which is perfluorinated or optionally substituted by a perfluoroalkyl group; a cycloalkyl group optionally substituted by an alkyl or alkoxy group; an aryl group optionally substituted by an alkyl or alkoxy group; an alkenyl group; an alkynyl group; or an arylalkyl group in which the aryl part is optionally substituted by an alkyl or alkoxy group; or else
    - T1 and T2 independently represent a monovalent radical of following formula (III):

            -V1-V2     (III)

    in which:
    • V1 is a saturated or unsaturated divalent hydrocarbon group which is optionally substituted,
    • V2 is a monovalent group chosen from the group of the following substituents:
    ◆ alkoxy, -ORa, with Ra corresponding to hydrogen, alkyl or aryl;
    ◆ silyl, -Si (ORb)x(Rc)3-x, with Rb corresponding to hydrogen, alkyl, silyl or siloxanyl, Rc corresponding to alkyl, aryl and x being an integer between 0 and 3;
    ◆ amine, or alternatively;
    - the substituents T1, T2, T3, T3', T4 and T4' can form, in pairs, when they are located on two adjacent ring members in the formulae (III) and (III'), a saturated or unsaturated hydrocarbon chain;
    - Z1 independently represents an anion derived from a Bronsted acid (protic acid)
    with as following conditions:
    - the choice of the strong base is made so as to be able to carry out a deprotonation of the hydrogen of the iminium functional group of structure (III) or (III') and is chosen from the group of the alkali metal and alkaline earth metal hydroxides, alkoxides, hydrides and amides,
    - the reaction is carried out in a solvent which is an alcohol or a mixture of alcohols, and the deprotonation produces a salt which precipitates and which is separated from the solution A.
  2. Process according to Claim 1, characterized in that the alcohol corresponds to the formula (I°) R°OH, in which R° corresponds to an alkyl, cycloalkyl, aryl, alkenyl, alkynyl, arylalkyl, silyl or siloxane group.
  3. Alcoholic solution A, characterized in that it is obtained according to the process as described according to either one of Claims 1 and 2 and consists of:
    Figure imgb0034
    • a solvent which is an alcohol or a mixture of alcohols,
    • which has the formula (II) or (II'):
    Figure imgb0035
     in which:
    - A and B independently represent C or N, it being understood that:
    • in the formula (II), when A represents N, then T4 is not present and, when B represents N, then T3 is not present;
    • in the formula (II'), when A represents N, then T4 or T4' is not present and, when B represents N, then T3 or T3' is not present;
    - T3, T3', T4 and T4' independently represent a hydrogen atom; an alkyl group; a cycloalkyl group optionally substituted by alkyl or alkoxy; an aryl group optionally substituted by alkyl or alkoxy; an alkenyl group; an alkynyl group; or an arylalkyl group in which the aryl part is optionally substituted by alkyl or alkoxy; or else
    - T3 and T4 can form, together and with A and B when the latter each represent a carbon atom, an aryl, it being understood that, in this case, T3' and T4' are not present;
    - T1 and T2 independently represent an alkyl group; an alkyl group optionally substituted by alkyl; an alkyl group which is perfluorinated or optionally substituted by a perfluoroalkyl group; a cycloalkyl group optionally substituted by alkyl or alkoxy; an aryl group optionally substituted by alkyl or alkoxy; an alkenyl group; an alkynyl group; or an arylalkyl group in which the aryl part is optionally substituted by alkyl or alkoxy; or else
    - T1 and T2 independently represent a monovalent radical of following formula (III):

            -V1-V2     (III)

    in which:
    • V1 is a saturated or unsaturated divalent hydrocarbon group,
    • V2 is a monovalent group chosen from the group of the following substituents:
    ◆ alkoxy, -ORa, with Ra corresponding to hydrogen, alkyl or aryl;
    ◆ silyl, -Si (ORb)x(Rc)3-x, with Rb corresponding to hydrogen, alkyl, silyl or siloxanyl, Rc corresponding to alkyl, aryl and x being an integer between 0 and 3;
    ◆ amine, alkyl or aryl; or alternatively;
    - the substituents T1, T2, T3, T3', T4 and T4' can form, in pairs, when they are located on two adjacent ring members in the formulae (II) and (II'), a saturated or unsaturated hydrocarbon chain.
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